supporting informationindividual experiment, by comparing the samples with the appropriate racemic...

New Journal of Chemistry

Supporting Information

Ce(OTf)3/PyBox Catalyzed Enantioselective Hosomi-Sakurai Reactions of

Aldehydes with Allyltrimethylsilane

Song Zhaoa, Xulong Zhang*a,b, Yuwei Zhanga, Huanhuan Yanga, Yan Huang*a, Kui Zhanga and

Ting Dua

a Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education & Xinjiang Uyghur

Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University,

Urumqi 830046, China.

b Technique Center of Xinjiang Entry-Exit Inspection and Quarantine Bureau, Urumqi 830063,

China.

* E-mail:[email protected]

Table of contents

General Information ........................................................................................................................S1

Catalyst Synthesis ...........................................................................................................................S2

Representative procedure for asymmetric allylation of aldehydes ..................................................S4

References .......................................................................................................................................S8

Copys of HPLC analysis of homoallylic alcohols ........................................................................ S10

Copys of 1H NMR and 13C NMR spectra ..................................................................................... S15

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015


S1

General Information

Unless otherwise stated, all reagents were purchased from commercial suppliers and used without

further purification. All solvents used in the reactions were distilled from appropriate drying

agents prior to use. Dichloromethane and trichloromethane were distilled from phosphorus

pentoxide immediately prior to use. THF and toluene were distilled from sodium benzophenone

ketone. Thionyl chloride and liquid aldehydes were purchased commercially and distilled before

use. The 4 Å molecular sieves were purchased in a powder form, crushed, sieved at 100 mesh

screen and then activated at 200oC for 4 h. Reactions were monitored by thin layer

chromatography (TLC) was performed on silica gel GF 254 (Qingdao, China). The TLC plates

were visualized by exposure to ultraviolet light and/or immersion in a staining solution

(phospho-molybdic acid) followed by heating on a hot plate. Flash column chromatography was

undertaken on silica gel (200-300 mesh; Qingdao, China) using a proper eluent. Melting points

were determined on a Yanaco MP-S3 micro melting point apparatus and are uncorrected. 1H NMR

and 13C NMR was recorded on a Varian Inova-400 in deuterated solvent. 1H chemical shifts are

reported in ppm (δ) with the TMS or solvent resonance employed as the internal standard (TMS, δ

0.00 ppm; CDCl3, δ 7.24 ppm). Data are reported as follows: chemical shift, number of equivalent

nuclei (by integration), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet,

br = broad, brs = broad singlet), coupling constant (Hz) and assignment. 13C chemical shifts are

reported in ppm (δ) with the TMS or solvent resonance employed as the internal standard (TMS, δ

0.00 ppm; CDCl3, δ 77.0 ppm). Optical rotations were measured on a Autopol VI automatic

polarimeter (Rudolph Research Analytical) and are reported as follows: concentration (c = g/dL),

and solvent. The enantiomeric ratios were determined by high performance liquid chromatography

(HPLC, Shimadzu LC-20AB) analysis employing a chiral stationary phase column specified in the

individual experiment, by comparing the samples with the appropriate racemic mixtures.

The following abbreviations are used throughout: ethyl acetate (EtOAc), dichloromethane

(CH2Cl2), chloroform (CHCl3), tetrahydrofuran (THF), isopropanol (IPA), enantiomeric excess

(ee), trimethylsilylchloride (TMSCl), melting point (m.p.), tetra-n-butylammonium fluoride

(TBAF), 2,6-bis(oxazolinyl)pyridine (Pybox).


S2

Catalyst Synthesis

Representative procedure for the synthesis of ligand PyBox-1~Pybox-4 (Scheme 1)

N COClClOC

i iii

R1 = H21

R1 = Ph ii iv

Pybox-1: R = i-PrPybox-2: R = Bn

i) amino alcohol, CH2Cl2, Et3N; ii) MsOH, CH2Cl2, reflux; iii) SOCl2, CHCl3, reflux; iv) NaOH, MeOH, rt

NO

ClNH HN

ClON

OOH

NH HNOH

O

R1

R1 R1R1

NN

O

N

O

PhPhPh

Ph

R R R R

R R

NN

O

N

O

R RPybox-3: R = i-PrPybox-4: R = Bn

2a: R = i-Pr, R1 = Ph2b: R = Bn, R1 = Ph2c: R = i-Pr, R1 = H2d: R = Bn, R1 = H

3

Scheme 1 synthesis of Pybox 1~Pybox 4

Pyridine-2,6-Dicarbonyl Dichloride (1) [1]. Pyridine-2, 6-dicarboxylic acid (0.418 g, 2.5 mmol)

was dissolved in thionyl chloride (5 mL ), the mixture was refluxed with stirring for 24 h under a

nitrogen atmosphere until a homogenous brown solution was obtained.. The excess thionyl

chloride was removed by distillation. The residue was placed under high vacuum for several hours

to afford pyridine-2,6-dicarbonyl dichloride (0.501 g, 98.2%) as pale cream crystals (m.p. 55-58

oC). The product was moisture sensitive and used directly in the next procedure.

Amido Alcohols (2) [2, 3]. To a stirred solution of (S)-amino alcohol [4, 5] (2.0 mmol) and Et3N (5.0

mmol, 0.7 mL) in CH2Cl2 (10 mL) was added dropwise a solution of pyridine-2,6-dicarbonyl

dichloride (1.0 mmol, 0.204 g) in 10 mL of CH2Cl2 at 0 oC, and the mixture was stirred for 12 h (0

oC to rt). The reaction mixture was diluted with CH2Cl2 (10 mL) and then washed sequentially

with aqueous NaHCO3 (15 mL), water (30 mL) and brine (15 mL). The organic layer was dried

with anhydrous Na2SO4. The filtrate was concentrated in vacuo, the residue was purified by

column chromatography over silica gel to give corresponding pure amido alcohols 2.

2,6-bis((S)-4,5-dihydro-4-isopropyl-5,5-diphenyloxazol-2-yl)pyridine (Pybox-1) [3b]. Compound

2a (0.11 mmol, 70.6 mg) and methansesulfonic acid (0.66 mmol, 63.4 mg) were dissolved in

CH2Cl2 (3 mL), the solution was refluxed for 6 h while keeping CaH2 in an addition funnel for

removing the water generated during the reaction. The reaction mixture was diluted with CH2Cl2


S3

(3 mL), washed sequentially with aqueous NaHCO3, water, and brine. The organic phase was

dried with anhydrous Na2SO4. The filtrate was concentrated in vacuo, the residue was purified by

column chromatography over silica gel to get the pure cyclized product Pybox-1(57.3 mg, yield

86%). White solid, m.p. 66-67 oC; [α]25D -252° (c 0.100, CHCl3); Rf = 0.48 (4:1 hexane:EtOAc);

1H NMR (CDCl3, 400 MHz): δ (ppm) 8.22 (2H, dd, J = 8.0 Hz, J = 3.6 Hz, H-3), 7.92 (1H, t, J =

8.0 Hz, H-4), 7.63 (4H, d, J = 7.6 Hz, J = 7.2 Hz, Ph), 7.42-7.31 (8H, m, Ph), 7.30-7.22 (8H, m,

Ph), 4.89 (2H, d, J = 4.8 Hz, H-4'), 1.95-1.90 (2H, m, CHCH3), 1.06 (6H, d, J = 6.8 Hz, CH3),

0.67 (6H, d, J = 6.4 Hz, CH3); 13C NMR (100 MHz, CDCl3): δ (ppm) 160.3 (C, C-2'), 146.8 (C,

C-2), 144.9 (C, Ph), 140.3(C, Ph), 137.7 (CH, C-4), 128.3(CH, Ph), 127.9 (CH, Ph), 127.7 (CH,

Ph), 127.3 (CH, Ph), 126.9 (CH, Ph), 126.3 (CH, Ph), 125.4 (CH, C-3), 93.7 (CH2, C-5'), 80.3

(CH, C-4'), 30.3 (CH, CHCH3), 21.9 (CH3), 17.3 (CH3).

2,6-bis((S)-4-benzyl-4,5-dihydro-5,5-diphenyloxazol-2-yl)pyridine (Pybox-2) [3b]. Using a

procedure similar to that described above for the preparation of Pybox-1 from bisamide 2b,

bisamide 2b (0.1 mmol, 73.8 mg) was treated with methansesulfonic acid (0.6 mmol, 57.7 mg) to

afford Pybox-2 (56.9 mg, 81%). White solid, m.p. 93-95 oC; [α]25D -361° (c 0.100, CHCl3); Rf =

0.4 (4:1 hexane:EtOAc); 1H NMR (CDCl3, 400 MHz): δ (ppm) 8.21 (2H, d, J = 7.6 Hz, H-3), 7.89

(1H, t, J = 8.0 Hz, H-4), 7.54 (4 H, dd, J = 8.4 Hz, J = 3.2 Hz, Ph), 7.37-7.09 (26H, m, Ph), 5.24

(2H, t, J = 7.2 Hz, J = 6.0 Hz, H-4'), 2.67 (4H, d, J = 6.8 Hz, CH2Ph). 13C NMR (100 MHz,

CDCl3): δ (ppm) 161.0 (C, C-2'), 147.3 (C, C-2), 143.8 (C, Ph), 140.3 (C, Ph), 138.8 (C, Ph),

137.3 (CH, C-4), 129.3 (CH, Ph), 128.4 (CH, Ph), 128.1 (CH, Ph), 127.9 (CH, Ph), 127.8 (CH,

Ph), 127.6 (CH, Ph), 127.1 (CH, Ph), 126.5 (CH, Ph), 126.1 (CH, Ph), 125.9 (CH, C-3), 93.7 (CH2,

C-5'), 67.0 (CH, C-4'), 40.0 (CH2, CH2Ph).

2,6-bis((S)-4,5-dihydro-4-isopropyloxazol-2-yl)pyridine (Pybox-3) [6]. Thionyl chloride (25.0

mmol, 1.9 mL) was added with stirring to a solution of compound 2c (2.0 mmol, 0.675 g) in

chloroform (15 mL). The mixture was heated under reflux for 3 h, then cooled in ice bath. Water

was added through the top of the condenser to quench the excess thionyl chloride and the aqueous

layer was extracted with dichloromethane (3×20 mL). The combined organic phases were washed

with saturated aqueous NaHCO3 (15 mL), water (30 mL) and brine (15 mL). The organic layer

was dried with anhydrous NaSO4. The filtrate was removed at reduced pressure to give compound

3 as a cream solid. The solid was dissolved in MeOH (15 mL) and treated immediately with


S4

aqueous NaOH (5.3 mL, 3 mol·L-1). The mixture was stirred at room temperature under a nitrogen

atmosphere for 3 days, and then extracted with dichloromethane (2×30 mL). The extract was

washed with water, brine and then dried with NaSO4. The filtrate was concentrated in vacuo, the

residue was purified by column chromatography over silica gel to get the pure cyclized product

Pybox-3 (0.374 g, yield 62%). White solid, m.p. 150-153 oC; [α]25D +124° (c 0.100, CH2Cl2) ; Rf

= 0.31 (2:1, CH2Cl2:EtOAc); 1H NMR (CDCl3, 400 MHz): δ (ppm) 8.22 (2H, d, J = 8.0 Hz, H-3),

7.87 (1H, dd, J = 8.0 Hz, J = 7.6 Hz, H-4), 4.54 (2H, dd, J = 9.6 Hz, J = 8.4 Hz, H-5'A), 4.25-4.22

(2H, m, H-5'B), 4.18-4.12 (2H, m, H-4'), 1.87 (2H, m, CHCH3), 1.05 (6H, d, J = 6.8 Hz, CH3),

0.94 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ (ppm) 162.2 (C, C-2'), 146.9 (C, C-2),

137.2 (CH, C-4), 125.7 (CH, C-3), 72.9 (CH2, C-5'), 71.0 (CH, C-4'), 32.8 (CH, CHCH3), 19.1

(CH3), 18.3 (CH3).

2,6-bis((S)-4-benzyl-4, 5-dihydrooxazol-2-yl)pyridine (Pybox-4) [6]. Using a procedure similar

to that described above for the preparation of Pybox-3 from bisamide 2d, bisamide 2d (0.5 mmol,

0.396 g) was treated with thionyl chloride to afford Pybox-4 (0.134 g, 67%).. White solid, m.p.

155-156 oC; [α]25D -58° (c 0.100, CH2Cl2); Rf = 0.25 (2:1 CH2Cl2:EtOAc); 1H NMR (CDCl3, 400

MHz): δ (ppm) 8.22 (2H, d, J = 7.6 Hz, H-3), 7.89 (1H, t, J = 8.0 Hz, J = 7.6 Hz, H-4), 7.33-7.22

(10H, m, Ph), 4.67-4.61 (2H, m, H-4'), 4.46 (2H, t, J = 8.8 Hz, H-5'A), 4.26 (2H, dd, J = 8.8 Hz, J

= 7.6 Hz, H-5'B), 3.27 (2H, dd, J = 13.6 Hz, J = 5.2 Hz, CHAHBPh), 2.74 (2H, dd, J = 13.6 Hz, J =

8.8 Hz, CHAHBPh); 13C NMR (100 MHz, CDCl3): δ (ppm) 162.6 (C, C-2'), 146.7 (C, C-2), 137.6

(C, Ph), 137.3 (CH, C-4), 129.1 (CH, Ph), 128.5 (CH, Ph), 126.5 (CH, Ph), 125.7 (CH, C-3), 72.5

(CH2, C-5'), 68.0 (CH, C-4'), 41.6 (CH2, CH2Ph).

Representative procedure for asymmetric allylation of aldehydes

To an oven dried 10 mL round-bottom flask equipped with a magnetic stirring bar was added

Ce(OTf)3 (23.5 mg, 0.04 mmol), 4Å molecular sieve (80 mg) and anhydrous CH2Cl2 (1 mL).

Pybox-1 (26.7 mg, 0.044 mmol) in CH2Cl2 (0.1 mL) was added and the mixture was stirred under

nitrogen atmosphere at room temperature for 2 hours to afford a light white suspension. A mixture

of benzaldehyde (21.2 mg, 0.2 mmol) and TMSCl (30.4 µL, 0.24 mmol) in CH2Cl2 (0.2 mL) was

added to the resulting suspension. The mixture was then cooled to 0 oC followed by the addition of

allyltrimethylsilane (63.5 µL, 0.4 mmol). The reaction mixture was stirred at room temperature for

30 h, then was quenched with saturated sodium bicarbonate solution (2 mL). The mixture was


S5

extracted with CH2Cl2 (3×10 mL), washed with brine, dried over Na2SO4, filtered and

concentrated in vacuo. The residual crude product was purified via silica gel (20:1 hexane:EA)

chromatography to afford the homoallylic alcohol as colorless oil.

OH

Compound 2a, (R)-1-phenylbut-3-en-1-ol, C10H12O, M=148.2, colorless viscous oil, [α]25D +50°

(c 0.100, CHCl3) [7]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.40-7.35 (3H, m, Ph), 7.32-7.28 (2H,

m, Ph), 5.87-5.79 (1H, m, H-3), 5.22-5.15 (2H, m, H-4), 4.76 (1H, dd, J = 7.6 Hz, J = 7.2 Hz,

H-1), 2.59-2.48 (2H, m, H-2), 2.08 (1H, brs, OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 143.8 (C,

Ph), 134.4 (CH, C-3), 128.4 (CH, Ph), 127.5 (CH, Ph), 125.8 (CH, Ph), 118.4(CH2, C-4), 73.3

(CH, C-1), 43.8 (CH2, C-2). Enantiomeric excess was determined by HPLC (Chiracel OD-H, 99:1

hexanes: isopropanol, 1.0 mL/min, 230 nm): tr (major) = 18.9 min, tr (minor) = 21.4 min.

OHH3C

Compound 2b, (R)-1-m-tolylbut-3-en-1-ol, C11H14O, M=162.2, colorless viscous oil, [α]25D +40°

(c 0.100, CH2Cl2) [8]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.24 (1H, dd, J = 7.6 Hz, J = 7.2 Hz,

Ar), 7.19-7.14 (2H, m, Ar), 7.09 (1H, d, J = 7.6 Hz, Ar), 5.85-5.77 (1H, m, H-3), 5.30-5.13 (2H, m,

H-4), 4.71 (1H, dd, J = 8.0 Hz, J = 5.6 Hz, H-1), 2.54-2.48 (2H, m, H-2), 2.37 (3H, s, CH3), 2.04

(1H, s, OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 143.9 (C, Ar), 138.1 (C, Ar), 134.6 (CH, C-3),

128.4 (CH, Ar), 128.3 (CH, Ar), 126.5 (CH, Ar), 122.9 (CH, Ar), 118.3 (CH2, C-4), 73.4 (CH,

C-1), 43.8 (CH2, C-2), 21.5 (CH3). Enantiomeric excess was determined by HPLC (Chiracel

OD-H, 98:2 hexanes:isopropanol, 0.6 mL/min, 254 nm): tr (major) = 16.5 min, tr (minor) = 22.1

min.

OH

H3C

Compound 2c, (R)-1-p-tolylbut-3-en-1-ol, C11H14O, M=162.2, colorless viscous oil, [α]25D +60°

(c 0.100, CH2Cl2) [8]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.25 (2H, dd, J = 6.0 Hz, J = 2.0 Hz,

Ar), 7.16 (2H, dd, J = 6.0 Hz, J = 2.0 Hz, Ar), 5.86-5.76 (1H, m, H-3), 5.19-5.11 (2H, m, H-4),

4.69 (1H, t, J = 6.4 Hz, H-1), 2.52-2.48 (2H, m, H-2), 2.35 (3H, s, CH3), 2.04 (1H, brs, OH). 13C


S6

NMR (100 MHz, CDCl3): δ (ppm) 140.9 (C, Ar), 137.1 (C, Ar), 134.6 (CH, C-3), 129.0 (CH, Ar),

125.7 (CH, Ar), 118.1 (CH2, C-4), 73.2 (CH, C-1), 43.7 (CH2, C-2), 21.1 (CH3). Enantiomeric

excess was determined by HPLC (Chiracel AS-H, 98:2 hexanes:isopropanol, 0.7 mL/min, 254 nm):

tr (major) = 14.1 min, tr (minor) = 15.8 min.

OH

OCH3

Compound 2d, (R)-1-(2-methoxyphenyl)but-3-en-1-ol, C11H14O2, M=178.2, colorless viscous oil,

[α]25D +42° (c 0.100, CH2Cl2) [8]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.33 (1H, dd, J = 7.6 Hz, J

= 1.6 Hz, Ar), 7.26-7.22 (1H, m, Ar), 6.96 (1H, td, J = 7.6 Hz, J = 1.2 Hz, Ar), 6.87 (1H, dd, J =

8.0 Hz, J = 1.2 Hz, Ar), 5.90-5.79 (1H, m, H-3), 5.16-5.08 (2H, m, H-4), 4.98-4.94 (1H, m, H-1),

3.85 (3H, s, OCH3), 2.62-2.46 (3H, m, H-2 and OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 156.3

(C, Ar), 135.2 (CH, C-3), 131.7 (C, Ar), 128.2 (CH, Ar), 126.8 (CH, Ar), 120.6 (CH, Ar), 117.5

(CH2, C-4), 110.4 (CH, Ar), 69.6 (CH, C-1), 55.2 (OCH3), 41.8 (CH2, C-2). Enantiomeric excess

was determined by HPLC (Chiracel OD-H, 98:2 hexanes:isopropanol, 0.8 mL/min, 254 nm): tr

(minor) = 16.8 min, tr (major) = 18.5 min.

OH

OCH3

Compound 2e, (R)-1-(3-methoxyphenyl)but-3-en-1-ol, C11H14O2, M=178.2, colorless viscous oil,

[α]25D +48° (c 0.100, CH2Cl2) [8]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.25 (1H, t, J = 8.0 Hz,

Ar), 6.94-6.91 (2H, m, Ar), 6.81 (1H, qd, J = 8.0 Hz, J = 2.8 Hz, J = 1.2 Hz, Ar), 5.85-5.75 (1H, m,

H-3), 5.19-5.12 (2H, m, H-4), 4.70 (1H, dd, J = 8.0 Hz, J = 1.6 Hz, H-1), 3.81 (3H, s, OCH3),

2.54-2.46 (2H, m, H-2), 2.09 (1H, brs, OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 159.7 (C,

Ar),145.6 (C, Ar), 134.4(CH, C-3), 129.4 (CH, Ar), 118.3 (CH, Ar), 118.0 (CH2, C-4), 112.9 (CH,

Ar), 111.3 (CH, Ar), 73.2 (CH, C-1), 55.2 (OCH3), 43.7 (CH2, C-2). Enantiomeric excess was

determined by HPLC (Chiracel OD-H, 98:2 hexanes:isopropanol, 1.0 mL/min, 254 nm): tr (major)

= 26.7 min, tr (minor) = 34.2 min.

OH

H3CO


S7

Compound 2f, (R)-1-(4-methoxyphenyl)but-3-en-1-ol, C11H14O2, M=178.2, colorless viscous oil,

[α]25D +56° (c 0.100, CHCl3) [7]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.28 (1H, dd, J = 6.8 Hz, J

= 2.0 Hz, Ar), 6.88 (1H, dd, J = 6.8 Hz, J = 2.0 Hz, Ar), 5.84-5.74 (1H, m, H-3), 5.18-5.11 (2H, m,

H-4), 4.68 (1H, t, J = 6.4 Hz, H-1), 3.80 (3H, s, OCH3), 2.52-2.48 (2H, m, H-2), 2.02 (1H, brs,

OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 159.0 (C, Ar), 136.0 (C, Ar), 134.6 (CH, C-3), 127.0

(CH, Ar), 118.2 (CH2, C-4), 113.8 (CH, Ar), 72.9 (CH, C-1), 55.2 (OCH3), 43.7 (CH2, C-2).

Enantiomeric excess was determined by HPLC (Chiracel OD-H, 95:5 hexanes:isopropanol, 0.8

mL/min, 230 nm): tr (minor) = 13.1 min, tr (major) = 13.9 min.

OH

CH3H3C

Compound 2g, (R)-1-(2,4-dimethylphenyl)but-3-en-1-ol, C12H16O, M=176.3, colorless viscous oil,

[α]25D +63° (c 0.100, CHCl3). 1H NMR (400 MHz, CDCl3): δ (ppm) 7.36 (1H, d, J = 8.0 Hz,

Ar), 7.04 (1H, d, J = 8.0 Hz, Ar), 6.96 (1H, s, Ar), 5.91-5.80 (1H, m, H-3), 5.20-5.13 (2H, m, H-4),

5.94 (1H, m, H-1), 2.52-2.41 (2H, m, H-2), 2.31 (3H, s, CH3), 2.30 (3H, s, CH3), 1.89 (1H, brs,

OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 138.9 (C, Ar), 136.8 (C, Ar), 134.9 (CH, C-3), 134.3

(C, Ar), 131.1 (CH, Ar), 126.9 (CH, Ar), 125.2 (CH, Ar), 118.1 (CH2, C-4), 69.6 (CH, C-1), 42.6

(CH2, C-2), 20.9 (CH3), 18.9 (CH3). Enantiomeric excess was determined by HPLC (Chiracel

OD-H, 95:5 hexanes:isopropanol, 0.8 mL/min, 220 nm): tr (major) = 8.0 min, tr (minor) = 8.8 min.

OH

Compound 2h, (R)-1-phenylhex-5-en-3-ol, C12H16O, M=176.3, colorless viscous oil, [α]25D +4° (c

0.100, CHCl3) [9]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.31-7.25 (2H, m, Ph), 7.22-7.17 (3H, m,

Ph), 5.87-5.77 (1H, m, H-5), 5.17-5.13 (2H, m, H-6), 3.68 (1H, m, H-3), 2.85-2.78 (1H, m, H-1A),

2.73-2.65 (1H, m, H-1B), 2.36-2.29 (1H, m, H-4A), 2.22-2.14 (1H, m, H-4B), 1.82-1.76 (2H, m,

H-2), 1.64 (1H, s, OH). 13C NMR (100 MHz, CDCl3): δ (ppm) 142.0 (C, Ph), 134.6 (CH, C-5),

128.4 (CH, Ph), 128.3 (CH, Ph), 125.8 (CH, Ph), 118.3 (CH2, C-6), 69.9 (CH, C-3), 42.0 (CH2, C-4),

38.4 (CH2, C-2), 32.0 (CH2, C-1). Enantiomeric excess was determined by HPLC (Chiracel OD-H,

95:5 hexanes:isopropanol, 1.0 mL/min, 254 nm): tr (major) = 5.5 min, tr (minor) = 10.5 min.


S8

OH

Compound 2i, (R)-1-(naphthalen-5-yl)but-3-en-1-ol, C14H14O, M=198.3, colorless viscous oil,

[α]25D +176° (c 0.100, CHCl3) [7]. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.08 (1H, d, J = 8.0 Hz,

Ar), 7.88 (1H, dd, J = 7.6 Hz, J = 1.6 Hz, Ar), 7.79 (1H, d, J = 8.4 Hz, Ar), 7.67 (1H, d, J = 7.2 Hz,

Ar), 7.56-7.47 (3H, m, Ar), 5.99-5.89 (1H, m, H-3), 5.53 (1H, m, H-1), 5.25-5.18 (2H, m, H-4),

2.80-2.74 (1H, m, H-2A), 2.65-2.58 (1H, m, H-2B), 2.28 (1H, d, J = 2.8 Hz, OH). 13C NMR (100

MHz, CDCl3): δ (ppm) 139.4 (C, Ar), 134.7 (CH, C-3), 133.7 (C, Ar), 130.2 (C, Ar), 128.9 (CH,

Ar), 127.9 (CH, Ar), 125.9 (CH, Ar), 125.4 (CH, Ar), 125.3 (CH, Ar), 122.9 (CH, Ar), 122.8 (CH,

Ar), 118.2 (CH2, C-4), 69.9 (CH, C-1), 42.8 (CH2, C-2). Enantiomeric excess was determined by

HPLC (Chiracel OD-H, 90:10 hexanes:isopropanol, 1.0 mL/min, 254 nm): tr (major) = 8.1 min, tr

(minor) = 13.9 min.

SOH

Compound 2j, (R)-1-(thiophen-2-yl)but-3-en-1-ol, C8H10OS, M=154.2, colorless viscous oil,

[α]25D +38° (c 0.100, CH2Cl2) [8]. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.25 (1H, dd, J = 4.8 Hz, J

= 1.6 Hz, Ar), 6.99-6.96 (2H, m, Ar), 5.88-5.78 (1H, m, H-3), 5.22-5.14 (2H, m, H-4), 5.05-4.96

(1H, m, H-1), 2.64-2.60 (2H, m, H-2), 2.34 (1H, d, J = 4.0 Hz, OH). 13C NMR (100 MHz, CDCl3):

δ (ppm) 147.8 (C, Ar), 133.8 (CH, C-3), 126.6 (CH, Ar), 124.5 (CH, Ar), 123.7 (CH, Ar), 118.8

(CH2, C-4), 69.3 (CH, C-1), 43.7 (CH2, C-2). Enantiomeric excess was determined by HPLC

(Chiracel OD-H, 97:3 hexanes:isopropanol, 0.6 mL/min, 220 nm): tr (major) = 19.8 min, tr (minor)

= 21.5 min.

References:

[1] H. Liu, X. Y. Jia, F. Wang, Q. Q. Dai, B. L. Wang, J. F. Bi, C. Y. Zhang, L. P. Zhao, C. X. Bai,

Y. M. Hu and X. Q. Zhang, Dalton Trans., 2013, 42, 13723.

[2] A. D. Gupta, D. Bhuniya and V. K. Singh, Tetrahedron, 1994, 50, 13725.

[3] (a) M. J. Totleben, J. S. Prasad, J. H. Simpson, S. H. Chan, D. J. Vanyo, D. E. Kuehner, R.

Deshpande and G. A. Kodersha, J. Org. Chem., 2001, 66, 1057; (3b) G. Sekar, A. DattaGupta and

Vinod K. Singh, J. Org. Chem., 1998, 63, 2961.


S9

[4] L. Qin, L. Li, L. Yi, C. S. Da and Y. F. Zhou, Chirality, 2011, 23, 527.

[5] Y. J. Wu, H. Y. Yun, Y. S. Wu, K. L. Ding and Y. Zhou, Tetrahedron: Asymmetry, 2000, 11,

3543.

[6] M. D. K. N. Towers, P. D. Woodgate and M. A. Brimble, Arkivoc, 2003, (i), 43.

[7] J. F. Traverse, Y. Zhao, A. H. Hoveyda and M. L. Snapper, Org. Lett., 2005, 7, 3151.

[8] T. Wang, X. Q. Hao, J. J. Huang, J. L. Niu, J. F. Gong and M. P. Song, J. Org. Chem., 2013, 78,

8712.

[9] N. Minowa and T. Mukaiyama, Bull. Chem. Soc. Jpn., 1987, 60, 3697.


S10

Copys of HPLC analysis of homoallylic alcohols Compound 2a: (R)-1-phenylbut-3-en-1-ol

Peak Ret. Time Area Height Area %

1 18.941 23239 305.7 26.4689

2 21.353 24547 295.4 73.5311


1 20.186 2944.3 78.3 100.000

Compound 2b: (R)-1-m-tolylbut-3-en-1-ol


1 19.892 15116.5 175.2 49.555

2 26.415 15388.1 166.3 50.445


1 16.478 190.7 7 11.159

2 22.071 1518.2 54.7 88.841


S11

Compound 2c: (R)-1-p-tolylbut-3-en-1-ol


1 14.568 3559.7 79.3 50.768

2 16.302 3490.9 84.3 49.232


1 14.085 83293.4 1627.8 94.765

2 15.788 4601.2 113 5.235

Compound 2d: (R)-1-(2-methoxyphenyl)but-3-en-1-ol


1 16.178 2033.2 76.3 48.676

2 17.356 2143.9 75.4 51.324


1 16.765 14 5.5E-1 4.225

2 18.476 316.6 12.4 95.775


S12

Compound 2e: (R)-1-(3-methoxyphenyl)but-3-en-1-ol


1 25.046 525.4 11.9 50.098

2 32.278 523.3 9.3 49.902


1 26.701 592.4 10.3 77.556

2 34.237 171.4 3.2 22.444

Compound 2f: (R)-1-(4-methoxyphenyl)but-3-en-1-ol


1 11.426 42335 2080.7 48.512

2 12.807 44932.6 1815.1 51.488


1 13.139 18.5 9.7E-1 6.787

2 13.909 254.6 11.6 93.213


S13

Compound 2g: (R)-1-(2,4-dimethylphenyl)but-3-en-1-ol


1 8.060 30095 1954.2 48.818

2 8.82 31552.5 1892 51.182


1 7.975 8486.1 737 94.897

2 8.769 456.3 37 5.103

Compound 2h: (R)-1-phenylhex-5-en-3-ol


1 8.5 1618 114.5 50.445

2 12.404 1589.4 73.8 49.555


1 5.476 5650.8 594.1 93.064

2 10.51 421.1 21.2 6.936


S14

Compound 2i: (R)-1-(naphthalen-5-yl)but-3-en-1-ol


1 7.933 36028.3 1995.4 47.267

2 13.111 40194.1 1433.2 52.733


1 8.109 9374.3 626.4 90.917

2 13.979 936.6 35.9 9.083

Compound 2j: (R)-1-(thiophen-2-yl)but-3-en-1-ol


1 18.566 65656.1 1654.3 49.236

2 20.320 6793.9 1531.1 50.764


1 19.836 2752.4 108.5 97.787

2 21.513 62.3 2.1 2.213


S15

Copys of 1H NMR and 13C NMR spectra


S16


S17


S18


S19


S20


S21


S22


S23


S24


S25


S26


S27


S28


S29


S30


S31


S32


S33


S34


S35


S36


S37


S38


S39


S40


S41


S42

supporting informationindividual experiment, by comparing the samples with the appropriate racemic...

Documents